Carbonylation of olefinically unsaturated compounds

ABSTRACT

Oxygenated organic compounds, e.g. esters, aldehydes, and amides, are prepared by reacting an olefinically unsaturated compound with carbon monoxide and a compound containing a replaceable hydrogen atom in the presence of a catalyst comprising cobalt or ruthenium carbonyl and a promoter ligand. The promoter ligand is selected from the group consisting of heterocyclic nitrogen compounds and phosphorus or sulfur oxides. These reactions are carried out under relatively mild conditions of temperature and pressure.

This is a division of application Ser. No. 973,069 filed Dec. 26, 1978.

BACKGROUND OF THE INVENTION

The present invention relates to a novel process for producingoxygenated organic compounds.

There are several known methods for producing oxygenated organiccompounds. The acid catalyzed (H₂ SO₄, HBF₄, etc.) synthesis ofcarboxylic acids or esters by the reaction of an olefinic substrate withCO and water or alcohol has been known since 1931. (J. Falbe, "CarbonMonoxide in Organic Synthesis", Springer-Verlag, New York (1970)).Although this process was used on a commercial scale it does haveserious limitations due to the reaction conditions and the isomericcomposition of the products.

A more commercially important synthesis of carboxylic acid/esters is thedirect carbonylation of olefinic substrates with CO and water/alcoholconducted in the presence of transition metals. In general, thiscarbonylation reaction, discovered by Repp in 1940 (I. Wender and P.Pino, "Organic Synthesis Via Metal Carbonyls", Volume 2, John Wiley, NewYork (1977)), involves the addition of carbon monoxide, carboxyl alkylor amide group (Y--H where Y equals --OR or --NHR and R is an alkyl),and an olefin.

However, when an unsymmetrical olefin is used as the substrate at leasttwo isomeric products are obtained. No general method has been developedfor the control of the isomeric product composition.

The present invention overcomes some of these problems present in theprior art. For example, the inventive process results in higherconversions, higher yields and faster reaction rates than thosedisclosed in the prior art. Furthermore, the instant process allows oneto obtain a high yield of a particular isomeric product composition.Thus, extremely high selectivities of particular oxygenated organiccompounds can be obtained by the inventive process.

Finally, the prior art carbonylation reactions operate under extremeconditions of temperature and pressure. In general, temperatures in therange of 160° C. to 300° C. and pressures in the range of 1,500 to 5,000psi are required. On the other hand, the present reaction may be carriedout under relatively mild conditions of temperature and pressure. Thisfurther advantage can result in substantial cost savings in theproduction of oxygenated organic compounds.

SUMMARY OF THE INVENTION

It has now been discovered that oxygenated organic compounds can beproduced by contacting an olefinically unsaturated compound with carbonmonoxide and a compound containing a replaceable hydrogen atom in thepresence of a catalyst comprising cobalt and/or ruthenium carbonyl and apromoter ligand selected from the group consisting of heterocyclicnitrogen compounds and phosphorus or sulfur oxides.

In particular, the inventive process results in high yields ofoxygenated compounds when operating at much lower temperatures andpressures than disclosed in the prior art. In addition, the productdistribution can be varied significantly by changing the CO/H₂ ratio,pressure, ligand, solvent, reaction time and other process variables.

Thus, the present invention provides a novel catalyst comprising apromoter ligand and at least one of cobalt and ruthenium carbonyl.Furthermore, the instant invention provides a novel process for theproduction of an oxygenated organic compound comprising contacting anolefinically unsaturated compound with carbon monoxide and a compoundcontaining a replaceable hydrogen atom in the presence of the abovecatalyst. Finally, the present invention provides a novel process forthe production of an oxygenated organic compound comprising contactingan olefinically unsaturated compound containing an alcohol moiety withcarbon monoxide in the presence of the above catalyst.

Specifically, the carbonylation reaction of acrylonitrile, carbonmonoxide, hydrogen gas, and methanol to yield methyl-β-cyanopropionateproceeds smoothly using a catalyst comprising cobalt carbonyl and aheterocyclic nitrogen oxide promoter ligand.

DETAILED DESCRIPTION

According to the present invention, improved yields and selectivities ofoxygenated organic compounds are obtained by contacting an olefinicallyunsaturated compound with carbon monoxide and a compound containing areplaceable hydrogen atom over a catalyst comprising cobalt and/orruthenium carbonyl and a promoter ligand selected from the groupconsisting of heterocyclic nitrogen compounds and phosphorus or sulfuroxides. The overall reaction taking place in this process is representedby the following equation: ##STR1## R₁₁, R₁₂ and Y are defined below.

Reactants

Olefinically unsaturated compounds which can be employed as reactants inthe inventive process have the following structure:

    R.sub.11 CH=CHR.sub.12

wherein R₁₁ and R₁₂ are each independently selected from:

(1) hydrogen (either R₁₁ or R₁₂ but not both);

(2) C₁₋₃₀ alkyl;

(3) --(CH₂)_(p) --CN, wherein p is 0-3; and

(4) --(CH₂)_(q) --OR₁₃, wherein q is 1-30 and R₁₃ is hydrogen or methyl.

Preferably, the olefinically unsaturated compounds comprise compoundswherein R₁₁ and R₁₂ are each independently selected from:

(1) hydrogen (either R₁₁ or R₁₂ but not both);

(2) C₁₋₁₀ alkyl;

(3) --(CH₂)_(p) --CN, wherein p is 0-2; and

(4) --(CH₂)_(q) --OH, wherein q is 1-10.

Most preferably, the olefinically unsaturated compounds comprisecompounds wherein R₁₁ and R₁₂ are each independently selected fromhydrogen (either R₁₁ or R₁₂ but not both), methyl and --(CH₂)_(p) --CN,wherein p is 0-1.

The second component in the inventive reaction system is a compoundcontaining a replaceable hydrogen atom. This compound can be representedby the following formula:

    H--Y

wherein Y is selected from the group consisting of:

(1) OR₁₄ wherein R₁₄ is a C₁₋₃₀ alkyl;

(2) ##STR2## wherein R₁₅ and R₁₆ are each independently selected fromC₁₋₁₀ alkyls; and

(3) H.

Preferably Y is selected from the group consisting of:

(1) OR₁₄ wherein R₁₄ is a C₁₋₁₀ alkyl;

(2) ##STR3## wherein R₁₅ and R₁₆ are each independently selected fromC₁₋₄ alkyls; and

(3) H.

More preferably Y is selected from the group consisting of:

(1) OR₁₄ wherein R₁₄ is a C₁₋₄ alkyl; and

(2) H.

The second component is most preferably either methanol or hydrogen.

In the embodiment of the invention in which H--Y is an alcohol or amine,it is preferred to add hydrogen gas to the reaction system. Preferablythe amount of hydrogen gas so added comprises less than 10% by volume ofthe total amount of the hydrogen gas and carbon monoxide gas in thereaction system. More preferably the hydrogen gas comprises 0.5% to 7.5%by volume of the hydrogen and carbon monoxide gas. The addition ofhydrogen gas can increase both the yield and selectivity to desiredproducts in this mode of the invention.

When H₂ is the compound containing a replaceable hydrogen atom then thereaction system will preferably contain 10% to 60% by volume hydrogengas based on the total volume of the carbon monoxide and hydrogen gas.More preferably the reaction system will contain about 50% hydrogen gas.

One way to supply carbon monoxide and hydrogen gas into the reactionsystem is in the form of synthesis gas. The amount of hydrogen in thesynthesis gas can be easily adjusted prior to insertion into thereactor.

The amount of carbon monoxide in the reaction system is not critical.Preferably the carbon monoxide is present in at least stoichiometricamounts and most preferably the carbon monoxide is present in amountsgreatly in excess of stoichiometric amounts. If desired, a carrier gaswhich is inert to the reactants, products and catalyst can be includedin the reaction system.

The molar ratio of the compound containing a replaceable hydrogen atomto the olefinically unsaturated compound can be 0.5-100:1 with a ratioof 1-10:1 being preferred. This ratio does not include the hydrogen gaswhich may be added to the reaction system when H-Y is an alcohol oramine.

In the embodiment of the invention in which the olefin reactant is analcohol (i.e. wherein R₁₁ or R₁₂ is --(CH₂)_(q) --OH), it has been foundthat the terminal hydrogen atom on the alcohol group will itself serveas a replaceable hydrogen atom. As a result, the alcohol moeity of theolefin will react with the olefinic double bond of the olefin therebyproducing a lactone. In this reaction system no H-Y component need beincluded since the olefin itself acts both as the olefin and the H-Ycomponent. The reaction in this particular system is shown by thefollowing equation:

    R.sub.11 CH=CHR.sub.12 +CO.sup.Cat. Lactone

wherein at least one of R₁₁ and R₁₂ is an alcohol.

PROCESS CONDITIONS

Generally, in carrying out the inventive process, the olefinicallyunsaturated compound, carbon monoxide, and the compound containing areplaceable hydrogen atom are contacted with one another in the liquidphase in the presence of the catalyst described below. The inventivereaction can be accomplished in the batch mode or continuously.

The reaction temperature is normally maintained between 50° C. to 150°C. and most preferably at about 100° C. The reaction pressure isnormally maintained at 100 to 2500 psi, preferably at 700 to 1000 psi.When the reaction is carried out in a batch mode, the reactants andcatalysts are contacted with one another for a period of ten minutesthrough six hours, and preferably one half hour to four hours. Areaction time of less than ten minutes or more than six hours can beused if desired although better results will be obtained if the reactiontime is maintained within this range. When the process is carried out ona continuous basis, the reaction catalyst contact time is normally 10seconds to 10 minutes, preferably 100 seconds to 5 minutes.

Both the rate of reaction and product distribution can be variedsignificantly by changing the process parameters. For example, normallyan increase in pressure increases the rate of reaction. However, at veryhigh pressures the reaction rate may decrease due to catalystdecomposition. Furthermore, the selectivity to a particular product maybe affected by pressure changes, e.g. in the carbonylation ofacrylonitrile there is an increase in the selectivity to then-cyanoester (3CE) as the pressure decreases.

A balance exists between temperature and pressure with respect tocatalyst decomposition. Generally, as the temperature increases the rateof reaction increases. However, an anomolous effect may occur due topartial catalyst decomposition. Thus, the temperature and pressure mustbe carefully adjusted.

Similarly, residence time has a large effect on homogeneous processes.For example, in the process for the carbonylation of acrylonitrile, theselectivity to methyl-β-cyanopropionate is much higher at short reactiontimes. Applicants surmise that the reduction in selectivity as afunction of reaction time is caused by the reduction of the ligand, e.g.4-picoline-N-oxide is reduced to 4-picoline. In view of the abovediscussion, it is clear that a particular reaction rate and productdistribution can be obtained by a careful adjustment of the processvariables.

CATALYSTS

The catalyst employed in the inventive process can be generallydescribed as one of two types. Both types comprise cobalt and/orruthenium carbonyl and a promoter ligand in an organic solvent. Thepromoter ligand is either a heterocyclic nitrogen compound or aphosphorus or sulfur oxide.

The nitrogen heterocyclic promoter ligand has the following structuure:##STR4##

wherein X is one of N and NO; and

wherein R₁, R₂, R₃, R₄, and R₅ are each independently selected from thegroup consisting of:

(1) H;

(2) C₁₋₁₀ alkyls;

(3) (CH₂)_(q) OH wherein q is 0-10;

(4) ##STR5## wherein s is 0-10; and (5) O(CH₂)_(t) CH₃ wherein t is0-10;

wherein R₁ and R₂ may comprise a five to eight membered carbocyclicfused ring optionally substituted with C₁₋₁₀ alkyls.

Preferably, X is NO, and R₁, R₂, R₃, R₄, and R₅ are selected from H,C₁₋₄ alkyls, CH₂ OH, OH, ##STR6## and OCH₃. Most preferably, R₁, R₂, R₃,R₄, and R₅ are selected from H, CH₃, and OCH₃.

The phosphorus or sulfur oxide promoter ligands have the followingformulae: ##STR7##

wherein R₆, R₇, R₈, R₉, and R₁₀ are each independently selected from:

(1) C₁₋₁₀ alkyls;

(2) polynuclear aryls containing up to 12 carbon atoms, optionallysubstituted with C₁₋₁₀ alkyls; and

(3) O(CH₂)_(t) CH₃, wherein t is 0-10; and wherein n is 0 or 1.

Preferably, R₆, R₇, R₈, R₉, and R₁₀ are each independently selected fromC₁₋₄ alkyls and most preferably R₆, R₇, R₈, R₉, and R₁₀ are CH₃.

The inventive catalyst can be prepared by mixing the cobalt and/orruthenium carbonyl with at least one promoter ligand in a solvent. Thecobalt and/or ruthenium carbonyl and the promoter ligand may be addedsimultaneously or separately to the solvent. The exact relationship inthe solvent between the cobalt and/or ruthenium carbonyl and thepromoter ligand is not known.

Any solvent in which the catalyst is soluble may be used in the presentinvention. Preferably, the solvent is an alcohol, aromatic, ester,nitrile and/or dinitrile. The solvent is most preferably an alcohol orester. In fact, the alcohol can be both a compound containing areplaceable hydrogen atom described above and the solvent. The preferredcatalyst concentration in the solvent is normally between 0.1% to 5% byweight.

The cobalt and/or ruthenium carbonyl can be added to the solvent in anyform from which cobalt and/or ruthenium carbonyl could be formed. Forexample, it is well known in the art that carbonyls can be formed fromnaphthalates, salts and nitrates and thus suitable naphthalates, saltsand nitrates can be added to the solvent to form a carbonyl compound insitu. Preferably, the catalyst contains cobalt carbonyl.

In general, the promoter ligand to cobalt and/or ruthenium carbonylmolar ratio is 0.1-50:1, preferably about 0.5-4, and most preferablyabout 2:1. This ratio will vary depending on the promoter ligand chosen.At high ligand to carbonyl ratios (i.e. 4:1) the rate of reactionsubstantially decreases even though selectivity to the desired productmay be increased. Thus, in the carbonylation of acrylonitrile, at highligand/carbonyl ratios the reaction rate decreases but the selectivityto methyl-β-cyanopropionate increases.

The catalyst of this invention is dissolved in the reaction medium as ahomogeneous catalyst. These homogeneous catalysts are prepared by knowntechniques. Specific preparations of these catalysts are shown in theworking examples of this specification. Broadly, however, the catalystsof this invention can be prepared by any of the techniques known in theart.

RECOVERY

The reaction product obtained upon completion of the reaction isnormally in the form of a liquid and composed primarily of unreactedreactants, catalyst and oxygenated organic compounds. This reactionproduct can be subjected to suitable known separation techniques, i.e.solvent extraction and fractional distillation, to yield the desired endproducts.

A particularly good method for separating the catalyst from the productsobtained in the present process is by the use of conjugate phaseextraction. In this separation scheme, the reaction effluent is treatedwith a C₅ to C₈ hydrocarbon which is miscible with the reaction solventbut which is a very poor solvent for the catalyst. Examples of suchhydrocarbons are pentane, hexane and octane. Enough of this hydrocarbonis added to the reactor effluent to separate almost all of the catalystinto one phase and a significant amount of products into the otherphase. Generally, this is between 1 to 4 volumes of hydrocarbon pervolume of reactor effluent.

It is desirable to exclude oxygen from this separation system so thatcatalyst decomposition will not occur. It is also desirable to minimizethe amounts of unreacted substrates in the reactor effluent prior totreatment with the hydrocarbon. This can be accomplished by simpledistillation or vacuum stripping. Finally, it is desirable to separatethe products and reactants as quickly as possible to reduce thepossibility of unwanted side reactions, e.g. methyl-β-cyanopropionatereacts with acrylonitrile to produce a dicyano ester.

The catalyst containing hydrocarbon phase can be diluted and recycledback to the reactor. The product phase is then subjected to knownseparation techniques such as distillation or extraction.

The oxygenated organic compounds produced by this process are useful asprecursors to polymers. The esters are also useful in perfumes,flavorings and pharmaceuticals. The aldehydes are useful as plasticizersand as intermediates for alcohols.

SPECIFIC EMBODIMENTS

In order to more thoroughly illustrate the present invention, thefollowing working examples are presented. In these examples, thefollowing definitions are used: ##EQU1## The results have all beenadjusted to a 100% carbon balance.

In general, the experimental method consists of placing a pre-weighedsolution of olefinically unsaturated compound, promoter ligand, compoundcontaining a replaceable hydrogen atom and solvent into a glasslinedautoclave. Next, cobalt carbonyl, Co₂ (CO)₈, is added and the autoclavesealed.

The autoclave is flushed two times with synthesis gas and then chargedwith the synthesis gas to the desired pressure. The temperature is thenincreased and the reaction proceeds for 1 to 4 hours. Occasionally,samples are withdrawn during the course of the reaction through the venttube and subjected to gas chromatography analysis. After the runs, theglasslined autoclave is brought to room temperature by cooling with coldwater, depressurized and opened for product analysis.

The results of the experiments are shown in Table I. A glossery of termsfollows Table I and specifies the meanings of the abbreviations used inTable I.

EXAMPLE 1

13.5 gms. of acrylonitrile, 0.88 gms. of 4-picoline-N-oxide, 9.78 gms.of methanol and 100 mls. of adiponitrile were placed in a glasslinedautoclave. Next, 1.37 gms. of Co₂ (CO)₈ were added and the autoclavesealed.

The autoclave was charged with synthesis gas containing 5% H₂ until apressure of 1,000 psi was reached. The temperature was set at 97.5° C.and the reaction proceeded for 90 minutes. The autoclave was thenbrought to room temperature by cooling with cold water, depressurizedand opened for product analysis. The product analysis is shown in TableI.

EXAMPLE 2

13.5 gms. of acrylonitrile, 0.88 gms. of 4-picoline-N-oxide and 100 mls.of methanol were placed in a glasslined autoclave. Next, 1.37 gms. ofCo₂ (CO)₈ were added and the autoclave sealed.

The autoclave was charged with synthesis gas containing 5% H₂ to apressure of 1,000 psi. The temperature was set at 97.5° C. and thereaction proceeded for 150 minutes. The autoclave was then brought toroom temperature by cooling with cold water, depressurized and openedfor product analysis. The product analysis is shown in Table I.

EXAMPLES 3 thru 80

The procedure outlined in Example 1 was followed with the molar ratio ofcobalt carbonyl/ligand, temperature, pressure, solvent and reaction timebeing varied. These variables are specified in Table I for each example.Table I also shows the product analysis for Examples 3 thru 80.

EXAMPLE 81

13.5 gms. of acrylonitrile, 0.75 gms. of pyridine-N-oxide and 100 mls.of methanol were placed into a glass-lined autoclave. Next, 1.37 gms. ofCo₂ (CO)₈ were added and the autoclave sealed.

The autoclave was charged with synthesis gas containing 5% H₂ to apressure of 800 psi. The temperature was set at 95° C. and the reactionproceeded for 60 minutes. The glasslined autoclave was then brought toroom temperature by cooling with cold water, depressurized and openedfor product analysis. The product analysis is shown in Table I.

EXAMPLE 82

This example followed the same procedure outlined in Example 81 exceptthat the temperature and reaction time were varied as set forth in TableI. The results are shown in Table I.

EXAMPLE 83

13.5 gms. of acrylonitrile, 0.88 gms. of 2-picoline-N-oxide and 100 mls.of methanol were placed in a glasslined autoclave. Next, 1.37 gms. ofCo₂ (CO)₈ were added and the autoclave sealed.

The autoclave was charged with synthesis gas containing 5% to a pressureof 800 psi. The temperature was set at 95° C. and the reaction proceededfor 120 minutes. The glasslined autoclave was then brought to roomtemperature by cooling with cold water, depressurized and opened forproduct analysis. The product analysis is shown in Table I.

EXAMPLES 84 THRU 97

The procedure outlined in Example 83 was followed except that the molarratio of cobalt carbonyl/ligand, solvent, ligand, temperature, pressureand reaction time were varied. These variables are specified in Table Ifor each example. Table I also shows the product analysis for Examples84 thru 97.

                                      TABLE I                                     __________________________________________________________________________    CARBONYLATION WITH HETEROCYCLIC NITROGEN COMPOUNDS                            Catalyst: Co.sub.2 (CO).sub.8 + Ligand                                        Unsaturated Olefin Feed: Acrylonitrile                                        Ex-       CO.sub.2                                                            am-       (CO).sub.8 /                                                                              Temp                                                                              Pres                                                                             Time                                                                              Conv                                                                              Yields (%)                               ple                                                                              Ligand Ligand                                                                            Solvent (°C.)                                                                      (psi)                                                                            (min)                                                                             (%) 3-CE                                                                             2-CE                                                                             PN 3-CPA                                                                             3-CPAA                                                                             3-MPN                                                                             Other              __________________________________________________________________________    1  4-PcNox                                                                              1:2 ADN + MeOH                                                                            97.5                                                                              1000                                                                             90  84.40                                                                             97.50                                                                            -- -- --  --   2.50                                                                              --                 2  4-PcNox                                                                              1:2 MeOH    97.5                                                                              1000                                                                             150 100.00                                                                            54.10                                                                            38.90                                                                            1.69                                                                             --  4.47 --  0.82               3  4-PcNox                                                                              1:2 ADN + MeOH                                                                            97.5                                                                              1000                                                                             180 80.80                                                                             62.90                                                                            35.50                                                                            -- --  --   1.60                                                                              --                 4  4-PcNox                                                                              1:2 MeOH    75  800                                                                              180 100.00                                                                            40.10                                                                            57.60                                                                            -- --  0.78 --  0.62               5  4-PcNox                                                                              1:2 DMP + MeOH                                                                            77.5                                                                              800                                                                              10  66.30                                                                             57.00                                                                            34.50                                                                            1.40                                                                             --  0.20 6.70                                                                              --                 6  4-PcNox                                                                              1:2 DMP + MeOH                                                                            77.5                                                                              800                                                                              60  100.00                                                                            52.40                                                                            41.10                                                                            0.90                                                                             --  1.50 4.20                                                                              --                 7  4-PcNox                                                                              1:2 MeOH    95  800                                                                              60  100.00                                                                            55.30                                                                            40.24                                                                            1.33                                                                             --  2.25 --  0.90               8  4-PcNox                                                                              1:4 MeOH    95  800                                                                              60  100.00                                                                            51.26                                                                            45.98                                                                            1.16                                                                             --  0.64 0.61                                                                              0.35               9  4-PcNox                                                                              1:1 MeOH    95  800                                                                              90  97.10                                                                             51.80                                                                            42.52                                                                            1.53                                                                             --  3.39 --  0.75               10 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              800                                                                              15  98.60                                                                             53.40                                                                            40.80                                                                            0.62                                                                             --  0.23 4.90                                                                              0.00               11.sup.1                                                                         4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              800                                                                              15  51.50                                                                             50.90                                                                            39.20                                                                            3.20                                                                             --  --   6.80                                                                              --                 12.sup.2                                                                         4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              800                                                                              20  99.50                                                                             47.40                                                                            33.80                                                                            1.90                                                                             11.23                                                                             1.73 3.90                                                                              --                 13 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              800                                                                              20  51.73                                                                             90.47                                                                            -- -- --  --   9.53                                                                              --                 14 4-PcNox                                                                              1:1 DMP + MeOH                                                                            97.5                                                                              800                                                                              25  99.90                                                                             40.50                                                                            40.50                                                                            -- 8.80                                                                              6.80 0.32                                                                              --                 15 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              800                                                                              30  70.49                                                                             91.50                                                                            -- -- --  --   7.94                                                                              0.56               16 4-PcNox                                                                              1:4 DMP + MeOH                                                                            97.5                                                                              800                                                                              35  99.10                                                                             52.30                                                                            38.70                                                                            0.50                                                                             --  0.40 8.10                                                                              --                 17.sup.1                                                                         4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              800                                                                              40  100.00                                                                            50.60                                                                            46.20                                                                            -- --  --   3.10                                                                              --                 18.sup.1                                                                         4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              800                                                                              45  99.95                                                                             51.30                                                                            44.30                                                                            0.50                                                                             --  0.50 3.40                                                                              --                 19 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              800                                                                              60  98.90                                                                             45.00                                                                            52.00                                                                            2.60                                                                             --  --   2.40                                                                              0.02               20.sup.3                                                                         4-PcNox                                                                              1:2 MeOH    97.5                                                                              800                                                                              60  100.00                                                                            54.50                                                                            38.70                                                                            2.00                                                                             --  2.00 --  2.70               21 4-PcNox                                                                              1:2 Benzene +                                                                             97.5                                                                              800                                                                              60  79.88                                                                             34.23                                                                            53.70                                                                            6.74                                                                             --  0.52 4.89                                                                              --                               MeOH                                                            22 4-PcNox                                                                              2:1 MeOH    97.5                                                                              800                                                                              90  100.00                                                                            40.20                                                                            45.20                                                                            1.98                                                                             --  12.00                                                                              0.30                                                                              0.26               23 4-PcNox                                                                              1:4 MeOH    97.5                                                                              800                                                                              90  100.00                                                                            51.75                                                                            43.54                                                                            1.46                                                                             --  0.80 --  2.45               24 4-PcNox                                                                              1:8 DMP + MeOH                                                                            97.5                                                                              800                                                                              115 99.90                                                                             67.70                                                                            21.60                                                                            -- --  0.62 10.10                                                                             --                 25 4-PcNox                                                                              2:1 MeOH    97.5                                                                              800                                                                              120 100.00                                                                            40.40                                                                            47.50                                                                            2.40                                                                             --  8.72 0.57                                                                              0.41               26 4-PcNox                                                                              1:2 MeOH    97.5                                                                              800                                                                              120 86.80                                                                             57.80                                                                            29.50                                                                            5.20                                                                             --  3.60 1.30                                                                              2.30               27 4-PcNox                                                                               1:16                                                                             DMP + MeOH                                                                            97.5                                                                              800                                                                              120 16.20                                                                             64.80                                                                            -- -- --  0.25 34.90                                                                             --                 28 4-PcNox                                                                              1:8 ADN + MeOH                                                                            97.5                                                                              800                                                                              150 22.60                                                                             53.70                                                                            20.70                                                                            -- --  --   25.60                                                                             --                 29 4-PcNox                                                                              1:1 ADN + MeOH                                                                            97.5                                                                              800                                                                              180 84.40                                                                             68.90                                                                            23.50                                                                            2.00                                                                             --  2.30 3.30                                                                              --                 30.sup.1                                                                         4-PcNox                                                                              1:2 MeOH    97.5                                                                              800                                                                              180 100.00                                                                            56.30                                                                            39.60                                                                            1.29                                                                             --  1.13 0.20                                                                              1.49               31.sup.4                                                                         4-PcNox                                                                              1:2 MeOH    97.5                                                                              800                                                                              180 48.10                                                                              9.73                                                                            -- -- --  --   84.20                                                                             6.04               32.sup.5                                                                         4-PcNox                                                                              1:2 MeOH    97.5                                                                              800                                                                              180 93.40                                                                             22.90                                                                            74.00                                                                            1.50                                                                             --  --   --  1.50               33.sup.6                                                                         4-PcNox                                                                              1:2 MeOH    97.5                                                                              800                                                                              180 100.00                                                                            48.90                                                                            48.00                                                                            1.20                                                                             --  0.30 0.80                                                                              0.80               34.sup.4                                                                         4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              800                                                                              180 91.10                                                                             39.90                                                                            53.90                                                                            Trace                                                                            --  0.40 5.30                                                                              --                 35 4-PcNox                                                                              1:8 MeOH    97.5                                                                              800                                                                              180 100.00                                                                            36.90                                                                            60.60                                                                            1.01                                                                             --  0.25 0.50                                                                              0.70               36 4-PcNox                                                                               1:16                                                                             MeOH    97.5                                                                              800                                                                              180 100.00                                                                            26.80                                                                            48.30                                                                            10.46                                                                            --  --   14.33                                                                             0.40               37 4-PcNox                                                                              1:2 MeOH    97.5                                                                              800                                                                              225 100.00                                                                            30.90                                                                            61.90                                                                            1.00                                                                             --  3.50 2.70                                                                              --                 38.sup.7                                                                         4-PcNox                                                                              1:2 MeOH    97.5                                                                              800                                                                              300 53.70                                                                             57.00                                                                            39.00                                                                            -- --  2.40 1.00                                                                              0.50               39 4-PcNox                                                                              1:4 MeOH    115 800                                                                              120 100.00                                                                            56.93                                                                            37.52                                                                            1.43                                                                             --  3.13 --  0.99               40 4-PcNox                                                                              1:2 DMP + MeOH                                                                            117.5                                                                             800                                                                              10  87.70                                                                             67.00                                                                            18.70                                                                            4.20                                                                             --  0.20 9.90                                                                              --                 41 4-PcNox                                                                              1:2 DMP + MeOH                                                                            117.5                                                                             800                                                                              60  100.00                                                                            52.40                                                                            38.20                                                                            1.90                                                                             --  2.80 4.60                                                                              --                 42 4-PcNox                                                                              1:2 MeOH    125 800                                                                              180 100.00                                                                            49.30                                                                            40.00                                                                            4.48                                                                             --  4.49 --  1.76               43 4-PcNox                                                                              1:2 MeOH    97.5                                                                              700                                                                              50  100.00                                                                            57.00                                                                            35.50                                                                            0.80                                                                             --  5.20 1.50                                                                              Trace              44 4-PcNox                                                                              1:2 ADN + MeOH                                                                            97.5                                                                              600                                                                              150 57.60                                                                             99.80                                                                            -- -- --  --   0.20                                                                              --                 45 4-PcNox                                                                              1:2 MeOH    97.5                                                                              600                                                                              180 100.00                                                                            56.30                                                                            37.80                                                                            2.01                                                                             --  2.21 1.15                                                                              0.54               46 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              500                                                                              120 99.70                                                                             55.90                                                                            40.30                                                                            1.50                                                                             --  0.60 --  1.60               47.sup.8                                                                         4-PcNox                                                                              1:2 DMP +  MeOH                                                                           85  400                                                                              170 74.60                                                                             60.80                                                                            35.10                                                                            -- --  --   3.90                                                                              0.19               48.sup.8                                                                         4-PcNox                                                                              1:2 DMP + MeOH                                                                            85  400                                                                              420 97.30                                                                             51.50                                                                            38.40                                                                            0.90                                                                             --  3.60 3.41                                                                              2.24               49 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              400                                                                              25  88.20                                                                             73.70                                                                            17.70                                                                            2.80                                                                             --  --   5.80                                                                              --                 50 4-PcNox                                                                              1:4 DMP + MeOH                                                                            97.5                                                                              400                                                                              25  51.51                                                                             82.36                                                                             7.95                                                                            -- --  --   9.13                                                                              0.56               51 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              400                                                                              40  97.30                                                                             70.90                                                                            21.30                                                                            2.10                                                                             --  0.40 5.30                                                                              --                 52 4-PcNox                                                                              1:4 DMP + MeOH                                                                            97.5                                                                              400                                                                              50  76.03                                                                             88.95                                                                             3.66                                                                            -- --  --   6.99                                                                              0.41               53 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              400                                                                              60  100.00                                                                            62.90                                                                            29.70                                                                            2.10                                                                             --  0.80 4.40                                                                              --                 54 4-PcNox                                                                              1:4 DMP + MeOH                                                                            97.5                                                                              400                                                                              60  67.95                                                                             81.56                                                                            11.36                                                                            -- --  --   6.68                                                                              0.40               55 4-PcNox                                                                              1:4 DMP + MeOH                                                                            97.5                                                                              400                                                                              150 91.95                                                                             81.01                                                                            11.16                                                                            0.81                                                                             --  --   6.67                                                                              0.35               56.sup.8                                                                         4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              400                                                                              180 49.70                                                                             92.30                                                                             0.10                                                                            -- --  --   5.32                                                                              2.30               57 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              400                                                                              285 55.70                                                                             89.27                                                                             0.63                                                                            5.35                                                                             --  --   4.53                                                                              0.22               58 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              400                                                                              300 62.12                                                                             86.80                                                                             0.73                                                                            5.42                                                                             --  1.53 4.61                                                                              0.87               59 4-PcNox                                                                              1:8 DMP + MeOH                                                                            117.5                                                                             400                                                                              120 47.50                                                                             74.56                                                                             0.17                                                                            -- --  0.23 19.95                                                                             5.09               60 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              300                                                                              15  69.70                                                                             89.90                                                                            -- 4.30                                                                             --  0.70 5.00                                                                              --                 61 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              300                                                                              20  24.40                                                                             86.90                                                                            -- -- --  --   5.00                                                                              8.10               62 4-PcNox                                                                              1:1 DMP + MeOH                                                                            97.5                                                                              300                                                                              25  85.60                                                                             87.60                                                                            -- 6.80                                                                             --  --   5.70                                                                              --                 63 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              300                                                                              25  46.80                                                                             93.80                                                                            -- -- --  --   6.20                                                                              --                 64 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              300                                                                              30  80.40                                                                             90.10                                                                            -- 3.60                                                                             --  --   6.31                                                                              --                 65 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              300                                                                              50  59.80                                                                             91.90                                                                            -- 2.60                                                                             --  --   5.20                                                                              --                 66 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              300                                                                              60  66.30                                                                             94.00                                                                            -- 0.20                                                                             --  --   5.80                                                                              --                 67 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              300                                                                              70  72.70                                                                             94.20                                                                            Trace                                                                            -- --  --   5.80                                                                              --                 68 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              300                                                                              90  79.10                                                                             91.70                                                                            Trace                                                                            2.30                                                                             --  0.40 5.60                                                                              --                 69 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              300                                                                              120 81.20                                                                             92.30                                                                            Trace                                                                            2.10                                                                             --  0.30 5.30                                                                              --                 70 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              300                                                                              140 88.70                                                                             92.50                                                                            Trace                                                                            2.10                                                                             --  0.60 4.80                                                                              --                 71 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              300                                                                              150 91.90                                                                             79.80                                                                            10.20                                                                            2.30                                                                             --  --   4.60                                                                              3.00               72 4-PcNox                                                                              1:8 DMP + MeOH                                                                            97.5                                                                              300                                                                              150 85.70                                                                             91.80                                                                             3.30                                                                            -- --  --   4.90                                                                              --                 73 4-PcNox                                                                              1:1 DMP + MeOH                                                                            97.5                                                                              300                                                                              180 91.10                                                                             72.20                                                                            18.20                                                                            5.30                                                                             --  --   4.30                                                                              --                 74 4-PcNox                                                                              1:2 DMP + MeOH                                                                            97.5                                                                              300                                                                              180 99.50                                                                             76.80                                                                            16.90                                                                            2.00                                                                             --  0.20 4.20                                                                              --                 75 4-PcNox                                                                              1:2 DMP + MeOH                                                                            117.5                                                                             300                                                                              25  58.80                                                                             82.40                                                                            -- 9.70                                                                             --  --   7.90                                                                              --                 76 4-PcNox                                                                              1:1 DMP + MeOH                                                                            117.5                                                                             300                                                                              120 38.44                                                                             77.32                                                                            -- 11.57                                                                            --  --   5.75                                                                              5.35               77 4-PcNox                                                                              1:8 DMP + MeOH                                                                            117.5                                                                             300                                                                              120 45.30                                                                             78.60                                                                            -- 11.60                                                                            --  --   7.50                                                                              2.40               78 4-PcNox                                                                              1:2 DMP + MeOH                                                                            117.5                                                                             300                                                                              150 63.30                                                                             80.70                                                                            -- 8.30                                                                             --  0.30 10.80                                                                             --                 79 4-PcNox                                                                              1:4 DMP + MeOH                                                                            117.5                                                                             300                                                                              180 87.40                                                                             93.40                                                                             6.00                                                                            -- --  --   0.50                                                                              --                 80 4-PcNox                                                                              1:8 DMP + MeOH                                                                            117.5                                                                             300                                                                              180 48.20                                                                             69.60                                                                            -- 13.20                                                                            --  --   13.60                                                                             3.70               81 PyNox  1:2 MeOH    95  800                                                                              60  100.00                                                                            31.58                                                                            62.38                                                                            2.14                                                                             --  3.54 0.06                                                                              0.31               82 PyNox  1:2 MeOH    97.5                                                                              800                                                                              180 100.00                                                                            52.40                                                                            42.20                                                                            1.50                                                                             --  3.10 --  --                 83 2-PcNox                                                                              1:2 MeOH    95  800                                                                              120 87.03                                                                              8.99                                                                            78.75                                                                            2.13                                                                             3.43                                                                              2.71 0.32                                                                              3.66               84 4-MPyNox                                                                             1:2 MeOH    95  800                                                                              90  100.0                                                                             45.68                                                                            51.96                                                                            0.91                                                                             --  0.99 0.19                                                                              0.27               85 4-MPyNox                                                                             1:2 DMP + MeOH                                                                            97.5                                                                              400                                                                              20  61.13                                                                             84.07                                                                            10.00                                                                            2.16                                                                             --  --   --  3.77               86 4-MPyNox                                                                             1:2 DMP + MeOH                                                                            97.5                                                                              800                                                                              10  69.40                                                                             65.50                                                                            30.50                                                                            -- --  4.00 --  --                 87 4-MPyNox                                                                             1:2 DMP + MeOH                                                                            97.5                                                                              800                                                                              20  94.30                                                                             55.50                                                                            41.00                                                                            1.00                                                                             --  2.50 --  --                 88 4-MPyNox                                                                             1:4 MeOH    97.5                                                                              800                                                                              90  97.40                                                                             34.50                                                                            62.30                                                                            0.99                                                                             --  0.28 2.10                                                                              0.12               89 4-MPyNox                                                                              1:16                                                                             MeOH    97.5                                                                              800                                                                              180 71.30                                                                             19.80                                                                            72.90                                                                            2.84                                                                             --  --   1.37                                                                              3.07               90 Pc acid                                                                              1:2 MeOH    97.5                                                                              800                                                                              180 42.30                                                                             24.10                                                                            -- -- --  6.90 23.50                                                                             45.40              91 3-Py Carb                                                                            1:2 DMP + MeOH                                                                            97.5                                                                              800                                                                              15  57.70                                                                             69.10                                                                            30.90                                                                            -- --  --   --  --                 92 3-Py Carb                                                                            1:2 DMP + MeOH                                                                            97.5                                                                              800                                                                              30  95.20                                                                             41.90                                                                            46.30                                                                            0.90                                                                             6.70                                                                              4.20 --  --                 93 3-Py Carb                                                                            1:2 MeOH    97.5                                                                              800                                                                              180 100.00                                                                            40.50                                                                            52.80                                                                            1.95                                                                             --  4.40 0.03                                                                              8.28               94 QuNox  1:2 MeOH    97.5                                                                              800                                                                              180 100.00                                                                             1.09                                                                            93.30                                                                            -- 0.67                                                                              4.58 0.07                                                                              0.27               95 t-but PyNox                                                                          1:2 DMP + MeOH                                                                            97.5                                                                              800                                                                              25  81.40                                                                             58.30                                                                            28.40                                                                            -- --  --   --  13.30              96 t-but PyNox                                                                          1:2 DMP + MeOH                                                                            97.5                                                                              800                                                                              60  100.00                                                                            40.80                                                                            51.50                                                                            0.20                                                                             --  --   --  7.30               97.sup.1                                                                         t-but PyNox                                                                          1:2 MeOH    97.5                                                                              800                                                                              180 100.00                                                                            50.50                                                                            46.80                                                                            1.30                                                                             --  0.60 0.30                                                                              0.40               __________________________________________________________________________     .sup.1 2.2% H.sub.2                                                           .sup.2 10% H.sub.2                                                            .sup.3 2 × Cat. Conc.                                                   .sup.4 0% H.sub.2                                                             .sup.5 Preformed in 5% H.sub.2 ; run on 0% H.sub.2                            .sup.6 1% H.sub.2                                                             .sup.7 1/10 × Cat. Conc.                                                .sup.8 1/2 Cat. Conc.                                                    

COMPOUND NAME ABBREVIATIONS

    ______________________________________                                        Abbreviation    Compound Name                                                 ______________________________________                                        ADN             adiponitrile                                                  BiPy-Nox        bipyridyl-di-N-oxide                                          2 CE            methyl-α-cyanopropionate                                3 CE            methyl-β-cyanopropionate                                 3 CPA           3-cyano-propionaldehyde                                       3 CPAA          3-cyano-propionaldehyde                                                       dimethyl acetal                                               DIABLO          diazabcyclo (2.2.2) octane                                    DMP             dimethylphthalate                                             DMSO            dimethyl sulfoxide                                            3-MPN           3-methoxy propionitrile                                       4-MPyNox        4-methoxy-pyridine-N-oxide                                    4-NPyNox        4-nitro-pyridine-N-oxide                                      Pc acid         picolinic acid-N-oxide                                        2-PcNox         2-picoline-N-oxide                                            4-PcNox         4-Picoline-N-oxide                                            PN              propionitrile                                                 PVPYRL          polyvinylpyrrolidone                                          3-Py Carb       3-pyridylcarbinol-N-oxide                                     PyNox           pyridine-N-oxide                                              QuNox           quinoline-N-oxide, dihydrate                                  TAD             tetraazadecane                                                t-but PyNox     4-t-butyl-pyridine-N-oxide                                    TEPO            triethyl phosphate oxide                                      TPPO            triphenylphosphine oxide                                      ______________________________________                                    

EXAMPLE 101

In each of the above example, methanol was used as the compoundcontaining a replaceable hydrogen atom. In the following examples,either t-butyl alcohol or n-amyl alcohol were used in place of methanol.

13.5 gms. of acrylonitrile, 0.88 gms. of 4-picoline-N-oxide and 100 mls.of t-butyl alcohol were placed into a glasslined autoclave. Next, 1.37gms. of Co₂ (CO)₈ were added and the autoclave sealed.

The autoclave was charged with synthesis gas containing 5% H₂ to apressure of 800 psi. The temperature was set at 97.5° C. and thereaction proceeded for 180 minutes. The glasslined autoclave was thenbrought to room temperature by cooling with cold water, depressurizedand opened for product analysis. The product analysis is shown in TableII.

EXAMPLES 102 AND 103

These examples follow the same procedure outlined in Example 101 exceptthat the solvent, alcohol and reaction time were varied. These variablesand the product analysis are shown in Table II.

EXAMPLES 104

In each of the above examples the unsaturated olefin feed wasacrylonitrile. In the following two examples, other olefins were fed tothe inventive reaction system.

5.26 gms. of propylene, 0.88 gms. of 4-picoline-N-oxide, 8.15 gms. ofmethanol and 100 mls. of orthoxylene were placed into a glasslinedautoclave. Next, 1.37 gms. of Co₂ (CO)₈ were added and the autoclavesealed.

The autoclave was charged with synthesis gas containing 5% H₂ to apressure of 800 psi.

                                      TABLE II                                    __________________________________________________________________________    CARBONYLATION WITH HETEROCYCLIC NITROGEN LIGAND                               Catalyst: Co.sub.2 (CO).sub.8 + Ligand                                        Unsaturated Olefin Feed: Acrylonitrile                                                                              Yields (%)                              Ex-      Co.sub.2 (CO).sub.8 /                                                                       Temp                                                                              Pres                                                                             Time                                                                              Conv         3-                             ample                                                                             Ligand                                                                             Ligand                                                                              Solvent (°C.)                                                                      (psi)                                                                            (min)                                                                             (%) 3-CE                                                                             2-CE                                                                             PN CPA                                                                              3-CPAA                                                                             3-MPN                                                                             Other              __________________________________________________________________________    101 4-PcNox                                                                            1:2   t-but   97.5                                                                              800                                                                              180 100.00                                                                             1.80                                                                            94.90                                                                            1.50                                                                             0.75                                                                             --   --  1.20                              alcohol                                                        102 4-PcNox                                                                            1:2   ADN + t-but                                                                           97.5                                                                              800                                                                              150 43.72                                                                             -- 87.39                                                                            -- -- --   --  12.61                             alcohol                                                        103 4-PcNox                                                                            1:2   ADN + n-amyl                                                                          97.5                                                                              800                                                                              180 55.62                                                                             39.70                                                                            0.61                                                                             1.99                                                                             -- 0.68 10.19                                                                             46.83                             alcohol                                                        __________________________________________________________________________

The temperature was set at 97.5° C. and the reaction proceeded for 180minutes. The glasslined autoclave was then brought to room temperatureby cooling with cold water, depressurized and opened for productanalysis. An 80% conversion of propylene was obtained with a 56% yieldof N-methylbutyrate and a 20% yield of methyl iso-butyrate.

EXAMPLE 105

14.8 gms. of allyl alcohol, 1.45 gms. of quinoline-N-oxide and 100 mls.of t-butyl alcohol were placed into a glasslined autoclave. Next, 1.37gms. of Co₂ (CO)₈ were added and the autoclave sealed.

The autoclave was charged with synthesis gas containing 5% H₂ to apressure of 800 psi. The temperature was set at 97.5° C. and thereaction proceeded for 180 minutes. The glasslined autoclave was thenbrought to room temperature by cooling with cold water, depressurizedand opened for product analysis. A 100% conversion of allyl alcohol wasobtained with a 50% yield of propionaldehyde and a 50% yield ofbutyrolactone.

EXAMPLE 106

Each of the above examples used a heterocyclic nitrogen ligand. Thefollowing examples use phosphorus or sulfur oxide ligands.

13.5 gms. of acrylonitrile, 1.46 gms. of triethylphosphateoxide and 100mls. of methanol were placed into a glasslined autoclave. Next, 1.37gms. of Co₂ (CO)₈ were added and the autoclave sealed.

The autoclave was charged with synthesis gas containing 5% H₂ to apressure of 800 psi. The temperature was set at 95° C. and the reactionproceeded for 180 minutes. The glasslined autoclave was then brought toroom temperature by cooling with cold water, depressurized and openedfor product analysis. The product analysis is shown in Table III.

EXAMPLES 107 THRU 109

The procedure outlined in Example 106 was followed with the temperature,reaction time and ligand being varied. These variables and the productanalysis are shown in Table III.

                                      TABLE III                                   __________________________________________________________________________    CARBONYLATION WITH PHOSPHORUS OR SULFUR ALKYL OXIDES                          Catalyst: Co.sub.2 (CO).sub.8 + Ligand                                        Unsaturated Olefin Feed: Acrylonitrile                                                  Co.sub.2 (CO).sub.8 /                                                                    Temp                                                                              Pres                                                                             Time                                                                              Conv                                                                              Yields (%)                                Example                                                                             Ligand                                                                            Ligand.sup.8                                                                        Solvent                                                                            (°C.)                                                                      (psi)                                                                            (min)                                                                             (%) 3-CE                                                                             2-CE                                                                             PN 3-CPA                                                                             3-CPAA                                                                             3-MPN                                                                              Other              __________________________________________________________________________    106   TEPO                                                                              1:2   MeOH 95  800                                                                              180 65.30                                                                             4.87                                                                             64.50                                                                            9.60                                                                             --  9.39 --   11.64              107   DMSO                                                                              1:2   MeOH 95  800                                                                              180 64.10                                                                             3.83                                                                             57.70                                                                            10.84                                                                            --  12.70                                                                              2.73 12.15              108   TPPO                                                                              1:2   MeOH 115 800                                                                               90 57.20                                                                             4.81                                                                             44.30                                                                            18.70                                                                            --  8.56 10.50                                                                              13.15              109   TPPO                                                                              1:2   MeOH 95  800                                                                              240 76.70                                                                             6.05                                                                             72.70                                                                            7.70                                                                             --  7.05 9.13 5.59               __________________________________________________________________________

Although only a few embodiments of the present invention have beenspecifically described above, it should be appreciated that manyadditions and modifications can be made without departing from thespirit and scope of the invention. These and all other modifications areintended to be included within the scope of the present invention, whichis to be limited only by the following claims:

We claim:
 1. A catalyst composition comprising a heterocyclic nitrogenpromoter ligand and at least one of cobalt carbonyl and rutheniumcarbonyl wherein said heterocyclic nitrogen promoter ligand has thefollowing structure: ##STR8## wherein X is NO; andwherein R₁, R₂, R₃, R₄and R₅ are each independently selected from the group consisting of: (1)H; (2) C₁₋₁₀ alkyls; (3) (CH₂)_(q) OH wherein q is 0-10; (4) ##STR9##wherein s is 0-10; and (5) O(CH₂)_(t) CH₃ wherein t is 0-10; andwhereinR₁ and R₂ may comprise a five to eight membered carbocyclic fused ringoptionally substituted with C₁₋₁₀ alkyls.
 2. The catalyst composition ofclaim 1 wherein R₁, R₂, R₃, R₄ and R₅ are each independently selectedfrom the group consisting of:(1) H; (2) C₁₋₄ alkyls; (3) (CH₂)_(q)OHwherein q is 0 or 1; (4) ##STR10## (5) OCH₃.
 3. The catalystcomposition of claim 2 wherein R₁, R₂, R₃, R₄ and R₅ are eachindependently selected from the group consisting of:(1) H; (2) C₁₋₄alkyls.
 4. The catalyst composition of claim 1 which contains cobalt. 5.The catalyst composition of claim 1 wherein the ligand and the cobalt orruthenium carbonyl are mixed with an inert organic solvent.